CN105592919A

CN105592919A - Hydrogenation reactor and process

Info

Publication number: CN105592919A
Application number: CN201480053533.4A
Authority: CN
Inventors: Z·纳瓦扎; F·巴克什
Original assignee: Saudi Basic Industries Corp
Current assignee: Saudi Basic Industries Corp
Priority date: 2013-09-06
Filing date: 2014-08-29
Publication date: 2016-05-18
Also published as: WO2015033231A2; US9902668B2; US20160214913A1; WO2015033231A3; EP3041915A2

Abstract

A reactor and process for removing unsaturated alkynes and diolefinic impurities from olefins and oxygenates is described.

Description

Hydrogenation reactor and technique

Background

Technical field

The disclosure relates to a kind of hydrogenation reactor and technique for removing unsaturated impurity from alkene and oxygenate.

Technical background

The selective hydrogenation of alkynes is indispensable technique in the purifying of alkene and oxygenate stream. Acetylene and two olefinic impuritiesInevitably be present in this type of stream, thereby and should be removed or reduce prevention catalyst poisoning satisfied becoming more meticulousThe target specification that the downstream of product and polymer produces. For example, ethylene stream can comprise approximately 0.1 % by mole to 3 % by mole conventionallyAcetylene, flow of propylene can comprise propine and/or the allene of approximately 0.5 % by mole to 10 % by mole conventionally. Ideally, these acetyleneThe concentration of impurity should be reduced to approximately 0.5 % by mole or lower level, and propine and/or allene impurity level should be lower than2.8 % by mole.

The common process of acetylene hydrogenation utilizes the catalyst of used additives modification, such as the catalyst based on Pd. Acetylene hydrogenationWell accepted mechanism be acetylene be adsorbed on the palladium metal site on catalyst and then with hydrogen reaction. Be used for adsorbing secondThe availability in the active palladium site of alkynes affects the selective of catalyst. Although ethene is to the hydrogenation of ethane from essence with comparatively fastSpeed occurs, if but exist a large amount of acetylene to be adsorbed onto on active palladium metal site, the selective suction of acetylene on palladium soAttachedly cause efficient acetylene hydrogenation.

Also can in front end acetylene converter, utilize the carbon monoxide of low concentration as reaction modifier. Carbon monoxide ratioAcetylene or conjugated diene are adsorbed onto on palladium more forcefully, even if therefore it also can stop ethene to be inhaled under low concentrationAttached.

The shortcoming of this type of hydrogenation/dehydrogenation technique comprises the generation of alkane, oligomer and the formation of coke. In conventional high-altitudeFor example, in the low haptoreaction (, hydrogenation and dehydrogenation) of speed, feed distribution and low pressure drop are desirable uniformly. May affect generationRate and optionally runaway reaction and focus are also very common.

Therefore, for example, removing from alkene and oxygenate in the technique of unsaturated impurity, continue to need new efficientlyFor reactor and the technique of hydrogenation and dehydrogenation reaction. Composition of the present disclosure and method meet these demands and other demands.

General introduction

According to the one object of the present invention (multiple object) of enforcement as concrete in this paper and overview description, the disclosure is a sideFace relates to hydrogenation reactor and the technique for removing unsaturated impurity from alkene and oxygenate.

On the one hand, the disclosure provides for remove alkynes, alkadienes and/or it from alkene and/or oxygenate streamThe integrated reactor design of mixture.

On the other hand, the disclosure provide for remove from alkene and/or oxygenate stream alkynes, alkadienes and/orThe integrated reactor design of their mixture, wherein hydrogenation under the existence of catalyst to occur minimum time of contact.

On the other hand, to provide the fast reaction of high production such as dehydrating alkanes be the useful reaction of alkene to the disclosureDevice design.

On the one hand, the disclosure provides the reactor being applicable in hydrogenation and/or dehydrogenating technology, and this reactor comprises:Catalyst bed, multiple imports for delivery of feed material to catalyst bed; And one or more outlets, wherein catalyst bedComprise and there is about 15m²/ g is to about 650m²The catalyst of the surface area of/g, and wherein this reactor can be provided for hydrogenation reactionApproximately 500/h to approximately 50, the air speed of 000/h or for the approximately 1/h of dehydrogenation reaction to approximately 1, the air speed of 000/h.

On the other hand, the disclosure provides the method for dehydrogenating technology, and the method comprises by multiple imports enteringMaterial material is incorporated in above-described reactor, makes feed material equably or contacts with catalyst bed equably substantiallyTo produce product.

On the other hand, the disclosure provides the method for hydrogenation technique, and the method comprises by multiple imports enteringMaterial material be incorporated in reactor claimed in claim 1, make feed material equably or substantially equably with catalystBench grafting touches to produce product.

Accompanying drawing summary

The accompanying drawing being incorporated in patent specification and form a part for patent specification has been set forth many aspects,And explain principle of the present invention together with description.

Fig. 1 illustrates the reactor design with two feed inlet and two outlets of the various aspects according to the present invention.

Fig. 2 illustrates the reactor design with two feed inlet and single outlet of the various aspects according to the present invention.

Fig. 3 illustrates the horizontal stroke of the reactor design with two feed inlet and two outlets of various aspects according to the present inventionSectional drawing.

What Fig. 4 illustrated according to the present invention various aspects has two feed inlet and two additional integrated cooling tubes of outletThe cross-sectional view of reactor design.

Fig. 5 illustrates the front end hydrogenation technique of the various aspects according to the present invention.

Fig. 6 illustrates the rear end hydrogenation technique of the various aspects according to the present invention.

Additional aspects of the present invention will partly state in the following description, and to a certain extent from descriptionIn apparent, or can know by putting into practice the present invention. Advantage of the present invention will be by means of special in appended claimsThe key element (element) of not pointing out and combination realize and obtain. Should be understood that aforesaid general remark and detailed description belowOnly all exemplary and explanatory, instead of to the restriction of the present invention of protecting as claim.

Invention is described

By describing and be included in embodiment wherein in detail with reference to below of the present invention, this can more easily be understoodBright.

Before disclosure and description the compounds of this invention, composition, article, system, device and/or method, should understand and removeNon-in addition concrete appointment, otherwise they are not limited to concrete synthetic method, unless or concrete appointment in addition, otherwise their offices notBe limited to predetermined substance (reagent), therefore they can change certainly. Should also be understood that term as used herein be only forParticular aspects is described, and without being intended to limit. Although any method similar or equivalent with material to method described hereinCan be used in practice of the present invention or test with material, but now describe exemplary method and material.

All publications mentioned in this article are all incorporated to herein by reference, are quoted with disclosure and description and publicationRelevant method and/or the material of content.

Definition

Unless otherwise defined, otherwise all technology used herein and scientific terminology all have with the present invention under fieldThe identical implication of common the understood implication of those of ordinary skill. Although similar with material or equivalent to method described hereinAny method and material can be used in practice of the present invention or test, but now describe exemplary method and material.

As used in patent specification and appended claims, singulative " (kind) " and " being somebody's turn to do (described) " bagDraw together plural number and refer to, unless context specifies in addition clearly. Thereby for example, " ketone " comprises the mixing of two kinds of ketone or more kinds of ketoneThing.

Scope can be expressed as in this article from " approximately " particular value and/or to " approximately " another particular value. Work as expressionWhen such scope, another aspect comprises from a particular value and/or to another particular value. Similarly, when using prefix" approximately ", while value representation being approximation, should understanding this particular value and form on the other hand. Should be further understood that the end points of each scopeRelevant with another end points and be all important irrelevant with another end points in the situation that. Should also be understood that and herein disclosed is many values,Each value, except being disclosed as particular value itself, is also disclosed as about this particular value herein. For example,, if openValue " 10 ", so also discloses " approximately 10 ". Should also be understood that the each unit also disclosing between two specific unit (unit).For example, if disclose 10 and 15, so also disclose 11,12,13 and 14.

As used herein term " optional " or " optionally " refer to that event or the situation next described can occurOr can not occur, and description comprises the situation that described event or situation occur and the feelings that described event or situation do not occurShape. For example, phrase " optionally substituted alkyl " refers to that this alkyl can be substituted or can not be substituted and description comprisesSubstituted alkyl and unsubstituted alkyl.

Disclose and be used for preparing the component of the present composition and by the composition being used in method disclosed hereinItself. These and other materials are disclosed in this article, and should be appreciated that, when the combination of these materials, subset, mutually doAll obtain when open with, group etc., although various independent combination and the concrete reference of set combination and the change of these compoundsChanging (permutation) may be clearly not open, but every kind has concrete consideration and description in this article. For example, asFruit discloses and has discussed specific compound and many repairing that can carry out the many molecules including this compound has been discussedDecorations, so unless the contrary is expressly indicated otherwise, otherwise have specifically considered every kind of combination of this compound and possible modification and have becomeChange. Therefore if disclose molecule A, B and C and molecule D, E and F, and the example A-of combination molecule is disclosed,D, so even without enumerating every kind separately, also independent and venue has been considered every kind, means combination A-E, A-F, B-D, B-E, B-F, C-D, C-E and C-F are regarded as open. Similarly, any subset of these combinations or combination also obtain open. Thereby,For example, the subgroup of A-E, B-F and C-E will be regarded as open. This concept is suitable for all aspects of the application, comprise but not officeBe limited to the step in the method for preparation and the use present composition. Thereby, if there are multiple additional steps to carry out, soEach step that should understand in these additional steps all can combine with any specific embodiments of the inventive method or embodimentCarry out together.

The weight of element-specific or component in the composition of mentioning in description and included claims or articleWeight in this element that part means to represent with weight portion or component and composition or article between any other element or componentRelation. Therefore, in the compound that contains 2 parts by weight of component X and 5 parts by weight of component Y, X and Y exist with the weight ratio of 2:5, andNo matter and whether this compound contain other component, X and Y all exist with this kind of ratio.

Unless have contrary clearly statement, otherwise the percentage by weight of component is included in preparation or group wherein based on componentThe gross weight of compound.

Unless have contrary clearly statement, otherwise as used herein term " air speed " is intended to refer to the body that enters of reactantThe business that long-pending flow rate obtains divided by reactor volume or catalyst bed volume. On the one hand, air speed can be indicated within the unit intervalCan process the number of feed material reactor volume.

As used herein term " alkyl " is branching or the non-branching saturated hydrocarbyl with 1 to 24 carbon atom, allAs methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, amyl group, hexyl, heptyl, octyl group, decyl, 14Alkyl, cetyl, eicosyl, tetracosyl etc. " low alkyl group " is the alkyl that contains 1 to 6 carbon atom.

As used herein term " alkoxyl " is the alkyl via single end ehter bond bonding; In other words " alcoxyl,Base " can be defined as-OR, wherein R is alkyl as defined above. " lower alkoxy " is the alkane that contains 1 to 6 carbon atomOxygen base.

As used herein term " thiazolinyl " is to have 2 to for example approximately 24 carbon atoms and have to comprise at least oneThe alkyl of the structural formula of carbon-to-carbon double bond. Dissymmetrical structure is intended to comprise E and Z isomers such as (AB) C=C (CD). This can push awayThe fixed structural formula that wherein has unsymmetrical alkenes in literary composition, or it can be explicitly pointed out by keysym C.

As used herein term " alkynyl " is to have 2 to for example approximately 24 carbon atoms and have to comprise at least oneThe alkyl of the structural formula of carbon-to-carbon triple bond.

As used herein term " aryl " is any aromatic group based on carbon, includes but not limited to benzene, naphthalene etc. ArtLanguage " aromatics " also comprises " heteroaryl ", and it is defined as the heteroatomic virtue at least one ring that is incorporated in aromatic groupFamily's group. Heteroatomic example includes but not limited to nitrogen, oxygen, sulphur and phosphorus. Aryl can be substituted or unsubstituted. ArylCan be replaced by one or more groups, described group include but not limited to alkyl, alkynyl, thiazolinyl, aryl, halide, nitro,Amino, ester, ketone, aldehyde, hydroxyl, carboxylic acid, or alkoxyl.

As used herein term " cycloalkyl " is the non-aromatic ring based on carbon, and it is made up of at least 3 carbon atoms.The example of cycloalkyl includes but not limited to cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl etc. Term " Heterocyclylalkyl " is to encircle extremelyA few carbon atom is by the cycloalkyl as hereinbefore defined that hetero atom replaced, described hetero atom such as, but not limited to nitrogen, oxygen,Sulphur, or phosphorus.

As used herein term " aralkyl " is such aryl, its have be connected in aromatic group as institute aboveAlkyl, the alkynyl of definition, or thiazolinyl. The example of aralkyl is benzyl.

As used herein term " hydroxyalkyl " is to have describing of at least one hydrogen atom being replaced by hydroxyl aboveAlkyl, thiazolinyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or Heterocyclylalkyl.

Term " alkoxyalkyl " is defined as at least one by hydrogen atom that above-described alkoxyl replacedAbove-described alkyl, thiazolinyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or Heterocyclylalkyl.

As used herein term " ester " represents by formula-C (O) OA, and wherein A can be above-described alkyl, halogenationAlkyl, thiazolinyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl group, Heterocyclylalkyl, or heterocycloalkenyl.

As used herein term " carbonate group " represents by chemical formula-OC (O) OR, and wherein R can be hydrogen, aboveAlkyl, thiazolinyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl or the Heterocyclylalkyl described.

As used herein term " carboxylic acid " is represented by formula-C (O) OH.

As used herein term " aldehyde " is represented by formula-C (O) H.

As used herein term " ketone group " represents by formula-C (O) R, and wherein R is above-described alkyl, thiazolinyl, alkynesBase, aryl, aralkyl, cycloalkyl, halogenated alkyl, or Heterocyclylalkyl.

As used herein term " carbonyl " is represented by formula C=O.

As used herein term " ether " is by formula AOA¹Represent wherein A and A¹Can be above-described alkane independentlyBase, halogenated alkyl, thiazolinyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl group, Heterocyclylalkyl, or heterocycloalkenyl.

As used herein term " sulfo group oxo base " is by formula-S (O)₂R、-OS(O)₂R, or-OS (O)₂OR represents, itsMiddle R can be hydrogen, above-described alkyl, thiazolinyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or Heterocyclylalkyl.

Every kind of material disclosed herein is all commercially available and/or its production method is well known by persons skilled in the art.

Should be understood that composition disclosed herein has some function. Herein disclosed is for carrying out certain of disclosed functionA little structural requirements, and should be understood that to exist and multiplely can carry out the structure that identical function is relevant to disclosed structure, and theseStructure can realize identical result conventionally.

As briefly described above, the disclosure provides the technique and the reactor that are used in hydrogenation and/or dehydrogenation reaction to establishMeter. On the one hand, this reactor design and/or technique can be used for removing unsaturated impurity from alkene and/or oxygenate stream.

On the one hand, the disclosure provide in the admixture of gas of for example alkene and/or oxygenate rich stream, remove toReactor and the technique of any unsaturated impurity that a few part may exist. In all fields, before reactor design can be used asEnd and/or rear end acetylene are removed unit (ARU) and are utilized. On the other hand, this kind of reactor can be used to from the alkene of for example etheneIn stream, remove acetylene.

On the one hand, reactor of the present disclosure can comprise commercial catalyst, and this depends on concrete mixing for example to be removedThe residing position of matter and described unit. On the one hand, reactor can utilize loaded catalyst. On the other hand, reactorCan utilize unsupported catalyst. On the other hand, reactor may be all useful for hydrogenation and dehydrogenating technology. Another sideFace, reactor comes in handy in the high-speed technique with low pressure drop. More on the one hand, reactor can provide exceed utilize normalRule reactor designs obtainable pliability (flexibility), to avoid runaway reaction and/or focus. By contrast, normalThe design of rule reactor may be subject to the impact of runaway reaction frequently.

In high-speed technique, such as, in hydrogenation and dehydrogenating technology, the uniformity of feed distribution can affect this work significantlySkill. Evenly or substantially charging uniformly can improve contacting and upset (turnover) of charging and catalyst, and at eachThe efficiency of this technique can be improved with selective in aspect. Thereby on the one hand, feed distribution is evenly or uniform substantially.

On the one hand, one or more reactors with identical or different configuration can use together. On the one hand, canTo use single-reactor. On the other hand, two or more reactors can for example make with serial or parallel connection arrangement formWith.

More on the one hand, reactor can be used in dehydrating alkanes fixed-bed process, for example, and so that alkane is changed into alkene.

Reactor described herein and technique can promote one or more to have the cross reaction of following characteristics: high-speed,Low pressure drop, good mobility, sane runaway reaction control, the control that focus is emerged or its combination.

For hydrogenation and/or dehydrogenation reaction, can utilize with one or more all such as the popular response device of acetylene hydrogenationAs the catalyst based on palladium of the additive modification of Ag, Ga, Ru, Ni, Pb, Sn, Bi, Sb, Au, Cu or its combination. Although do not wishBound by theory, is adsorbed onto on the palladium metal site on catalyst but well accepted mechanism is acetylene. The acetylene of absorption can quiltCatalyst activation and and hydrogen reaction. The selective availability control that on the one hand can receptor 1 activity palladium metal site of reaction.Although the intrinsic speed of ethylene hydrogenation is greater than acetylene, if there is the palladium metal site in a large amount of acetylene and catalyst bedContact, acetylene is adsorbed on palladium more forcefully so, causes the high selectivity towards acetylene hydrogenation.

In all fields, reactor of the present disclosure can front-end configuration, the form of backend arrangement or its combination uses. FrontIn end configuration, hydrogenation reactor can be arranged on the compressor bank of cracked gas before hydrogen, methane and carbon monoxide are removed(train) in, and can for example be arranged on C₂Separator below and can be arranged on demethanator before. ForThe feed material of this kind of front-end configuration can comprise acetylene and/or olefin(e) compound, and (for example approximately 12 % by mole of a large amount of hydrogenTo approximately 45 % by mole). For the typical H of this kind of configuration₂/ alkynes ratio can be approximately 5 to approximately 50 scope, wherein carbon monoxideConcentration at about 50ppm to approximately 5, in the scope of 000ppm. The reverse water-gas shift reaction of carbon monoxide from cracking funace forms, alsoBecause like this, carbonomonoxide concentration can change. It shall yet further be noted that the value of enumerating for feed material is only intended to illustrate herein,The present invention has no intention to be confined to any specific components and/or concentration value.

In backend arrangement, reactor can arrange after for example hydrogen, methane and/or carbon monoxide are removed step.Therefore, can by approximately 1 volume % to the hydrogen of approximately 4 volume % and carbon monoxide join in reactor feed or by they pointOpen and be injected in reactor. On the one hand, front-end and back-end reactor can be at for example room temperature bar of approximately 20 DEG C to approximately 40 DEG CPart and turning round to the pressure within the scope of approximately 30 bar at approximately 15 bar. The execution of any given reactor or reaction all may be subject to allAs Hg, O₂、COS、H₂S、NH₃、PH₃Affect with the existence of the impurity of other compounds. In addition, the hydrogen of low ratio and acetyleneMay provide higher ethane selective, because may not have abundant acetylene to contact with all catalyst site.

Reactor

Reactor of the present disclosure and technique can be used separately or make with other assemblies, reactor and/or process combinationWith. In all fields, reactor and/or its any assembly can comprise any be applicable to as described herein hydrogenation and/orMaterial in dehydrogenation reaction. On the one hand, the construction material of this kind of reactor for any feed material, reactant, catalyst,Product, accessory substance, or other chemical compounds that can contact with reactor during running well are inertia or are substantially lazyProperty. On the one hand, all or part of of reactor can for example be made lining with fragment of brick and/or ceramic material in inside. At anotherAspect, reactor or its part can by any be adapted under process conditions using and be applicable to the given reactant reacting withThe material that product uses is together built. On the other hand, reactor or its part can comprise stainless steel, such as, 304 is stainlessSteel and/or 316 stainless steels.

On the other hand, the size of reactor or its any part can change, and this depends on concrete feed material, productWith the scale of operation of expecting. Having those skilled in the art of the present disclosure can easily go out for given reaction or process choiceThere is reactor or the assembly of suitable dimension.

On the one hand, reactor can comprise closed container, and it has one or more imports and one or more outlet. ?On the other hand, reactor can comprise the catalyst bed that is installed in internal tank, and it is configured to make feed material and catalystBench grafting touches and residue feed material and/or product are flowed through and/or flow through catalyst bed.

Reactor can comprise the multiple imports that feed material can be sent and/or is dispensed to catalyst bed. Each sideFace, reactor comprises 2,3,4 or more import. On the other hand, each import all can be configured to feed material to leadGuide on the first side of catalyst or catalyst bed or its part. On the one hand, reactor comprises 2 imports. The opposing partyFace, reactor comprises 3 imports. More on the one hand, reactor comprises 4 imports. On the one hand, can make feed material flow manyIndividual, for example, thereby 2,3,4 or more import between cut apart feed material be assigned to whole of catalyst or catalyst bedOn one side. On the other hand, all or part of of multiple imports can be configured to feed material flow point to be slit into multipleThe homogeneous turbulence such as be equal to or approximate. On the other hand, reactor comprises multiple entering for the separate reactors in technique or stageMouthful.

Any one or more (if existence) in multiple imports optionally comprise for disperseing one of feed materialIndividual or multiple distributors. Distributor can comprise any for distributing and/or disperse the device of the feed material in reaction vessel. ?Various aspects, distributor can comprise porous ceramic film material, sintering metal, have conduit or its combination of multiple openings. At otherAspect, but distributor can comprise that other do not enumerate the material and/or the configuration that dispersible feed material herein. On the one hand, manyEach in individual import all can comprise multiple distributors. On the other hand, use distributor can improve towards catalyst and/Or the feed material of catalyst bed stream, feed material is contacted with catalyst bed more equably. More on the one hand, feed materialStream can be uniformly or uniform substantially on whole first side of catalyst or catalyst bed. As used hereinTerm is intended to describe such aspect substantially uniformly, wherein feed material stream on the whole first surface of catalyst bed allApproximate being equal to. Aspect such, stream and/or concentration still can there is little variation, but with there is single importComparable stream compare significantly less and/or less.

Reactor of the present disclosure can have single or multiple outlet. On the one hand, reactor can comprise single outlet. ?On the other hand, reactor can comprise multiple, such as, 2,3,4 or more outlet. On the one hand, reactor comprises multiple outlets,And any two or more outlets can be at the synthetic single stream of downstream group. On the other hand, each outlet all can be configured toCollect the stream from the second side of catalyst bed the side of the first side opposition (with). Aspect such, the catalysis of flowing throughAgent and/or catalyst bed and/or contact with catalyst and/or catalyst bed after unreacted feed material, product,And/or accessory substance can utilize one or more outlets to collect.

On the one hand, reactor can also comprise one or more be used for collecting condensate and/or oil, for example paraffinic base crude oilsPosition. According to the geometric orientation of reactor, (multiple) bleeding point can be configured to via gravity collect condensate and/Or oil. Thereby on the one hand, bleeding point can provide the bottom at reactor vessel. On the other hand, reactor vessel can be byBe designed so that any condensate and/or the oil producing and/or reclaim will flow to one or more bleeding points. For example, reactorBottom can be bowl shape, to collect condensate and/or oil at single point. On the other hand, can be sharp in reactorWith plate-like vessel and/or auxiliary condensate and/or the oil collected of a dish.

The catalyst using in specific reaction can carry out according to the product of concrete reaction, feed material, impurity and expectationSelect. In all fields, catalyst can be installed in bed, and feed material is contacted with catalyst bed. On the one hand, catalysisAgent bed is installed between multiple imports of reactor and one or more outlets of reactor. Catalyst bed can have any suitableClose the thickness using in together with specific reaction. On the one hand, catalyst bed does not significantly hinder feed material and/or reaction productLogistics is through reactor (, from import to outlet). On the other hand, catalyst bed can contact with the inwall of reactor, therebyFeed material stream from import and the reacting product stream that leads to one (multiple) outlet are separated. Reactor can be designedBecome to make to exist between import and catalyst bed first gas compartment, and existence between catalyst bed and one (multiple) outletSecond gas compartment. On the one hand, for example gas compartment between import and catalyst bed of this kind can make feed materialEasily be distributed in whole catalyst bed.

One or more somes place support catalyst bed that can be in reactor. On the one hand, can use multiple supporters to incite somebody to actionCatalyst bed is arranged in reactor and prevents mobile. Aspect concrete, reactor can be designed to have and be installed in top surfaceOn import and one (multiple) be installed in the outlet on basal surface. Aspect such, catalyst bed can flatly be installed inIn reactor, support with multiple supporters between catalyst bed basal surface and inside reactor diapire. It should be noted thatThis aspect is only intended to illustrate, and does not imply concrete geometric orientation or does not have concrete geometric orientation to be considered to be thisBright essential. The composition of catalyst bed can comprise conventional use or art technology people in hydrogenation and/or dehydrogenation reactionMember's qualification is for any suitable catalyst and/or the backing material of this kind of reaction. The antigravity system of hydrogenation and dehydrogenation reactionIt is known and commercially available acquisition.

During use and according to concrete reaction and the catalyst that uses, catalyst bed and/or reactor can showGo out variations in temperature. For exothermic reaction, catalyst bed and/or reactor can show significantly increasing of temperature. Similarly, forThe endothermic reaction, catalyst bed and/or reactor can show the remarkable reduction of temperature. For some reactions and/or catalyst systemSystem, in order to raise the efficiency or in order to prevent that catalyst from suffering damage, reactor and/or catalyst bed temperature to be maintained to targetIn scope, may be important. Thereby on the one hand, reactor can comprise one or more can be used for measuring reactor or catalysisThe thermocouple sheath of the temperature in agent bed. On the one hand, this type of thermocouple sheath can be configured to the outer surface from reactorExtend to the position in catalyst bed. The ability of the temperature in monitoring reactor is at optimization efficiency and prevent catalyst or reactorOverheated or the damage aspect of assembly comes in handy.

On the other hand, can adopt for heating and/or the mechanism of cooled catalyst bed and/or reactor. At eachAspect, Ci Zhong mechanism can comprise for heating or heating element heater or the pipe of cooled catalyst bed. On the other hand, can utilize and appointThe temperature of the device control what is suitable and/or adjusting reactor or catalyst bed. On the one hand, pipe can be installed in catalyst bedIn, wherein fluid, the temperature of adjusting catalyst bed thereby for example water can flow. On the one hand, single rolling tube or multiple pipe canBe installed in catalyst bed, thereby wherein fluid can flow through the temperature that reduces catalyst bed from pipe. While needs, fluid can be optionalGround in addition cooling and/or recirculation to maintain desirable temperature in catalyst bed.

On the one hand, reactor can front-end configuration form utilize. Aspect such, reactor can be in hydrogen, firstAlkane and carbon monoxide are arranged in the compressor bank of cracked gas before removing. On the other hand, reactor can be arranged on C₂CrackingThe downstream of device. More on the one hand, reactor can be arranged on the upstream of demethanator. In the time using with front end collocation form, enterMaterial material can comprise alkynes and/or olefin(e) compound. On the one hand, this kind of feed material can comprise a large amount of hydrogen (for example approximately 12% by mole to approximately 45 % by mole).

On the other hand, reactor can backend arrangement form utilize. Aspect such, reactor can be arranged on hydrogenGas, methane and/or carbon monoxide are removed the downstream of unit. On the one hand, the downstream that reactor can be arranged on hydrogen removes unit,Make hydrogen in reactor feed, account for approximately 1 volume % to approximately 4 volume %. On the other hand, reactor can be arranged on an oxygenChange carbon downstream or other places of removing unit, make not exist in charging carbon monoxide or have minute quantity carbon monoxide. ?Such aspect, is joined in reactor feed before can be in carbon monoxide is joined to reactor, or by oneCarbonoxide is directly injected in reactor.

In other respects, reactor can operate in a continuous manner, wherein has stable feed material stream. The opposing partyFace, reactor can intermittent mode operation, wherein specified rate feed material is in single pulse mode or at a fixed time in sectionInject by multiple imports, feed material stream will stop advancing after this. More on the one hand, reactor can Semi-batch Process behaviourDo, wherein a part for reactor can be used by operation mode, and the unitary part of reactor operates with regeneration mode. Like thisAspect, one or more imports can be in operation mode, and other one or more imports can be simultaneously or with for exampleAlternate cycles mode is for regeneration. Aspect such, as required, catalyst or its part can not exclusively stop techniqueSituation under regenerate. In operating aspect, one or more dispensers or baffle plate can be used for reactor in reactorEach several part is kept apart and is allowed running operation and regenerative operation separately, simultaneously.

As noted, multiple separate reactors can be connected and/or collocation form utilization in parallel. In all fields,Can in technique, use 2,3,4,5,6,7,8,9,10, or more separate reactors. At exemplary double bed reactor assemblyIn, two reactors are in series installed by front-end configuration form. This example system can be for the hydrogenation of for example acetylene. ForDepropanizer application, can utilize approximately 2 to approximately 4, for example, and 2,3 or 4 separate reactors. On the one hand, do not expect componentConcentrated may make to become to the reactor of determined number essential. In similar aspect, when for dehydrogenation reaction, approximately 1 to for example approximately10 reactors can parallel way utilization.

In other respects, the invention is intended to contain hydrogenation and/or dehydrogenating technology, wherein feed material is via multiple imports,For example 2,3,4,5,6 or more import be delivered to reactor, catalyst and/or catalyst bed. On the other hand, the present invention's meaningContaining hydrogenation and/or dehydrogenating technology, wherein product, accessory substance and/or unreacted feed material are via 1,2,3 or moreMultiple outlets are carried from reactor, catalyst and/or catalyst bed.

In all fields, reactor can be used as the front end and/or the rear end acetylene that contain ethene or other olefin streams and removes listUnit, for example, utilize with serial or parallel connection collocation form. On the other hand, reactor can be used on for alkane being changed into alkeneIn dehydrating alkanes fixed-bed process. On the one hand, reactor design described herein can provide following one or more:The stream of high-speed, low pressure drop, improvement distributes, and/or the control to runaway reaction and/or the prevention that improve. In other respects, originallyLiterary composition in described benefit any two or more, three or more, or four can the application of the invention reactionDevice obtains.

On the one hand, reactor and/or hydrogenation technique can turn round under following air speed: about 500/h is to approximately 50,000/H, for example about 500/h, 1,000/h, 2,000/h, 3,000/h, 4,000/h, 5,000/h, 10,000/h, 15,000/h, 20,000/h, 25,000/h, 30,000/h, 35,000/h, 40,000/h, 45,000/h, or 50,000/h; Approximately 1,000/h extremely approximately50,000/h; Approximately 10,000/h is to approximately 50,000/h; Approximately 20,000/h is to approximately 50,000/h; Or approximately 30,000/h is to approximately 50,000/h, this depends on the special catalyst that for example used and the temperature of reactor and/or catalyst bed. On the one hand, reactionDevice and/or hydrogenation technique can be at approximately 20 DEG C to approximately 200 DEG C, for example approximately 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C or 200 DEG CAt temperature, turn round.

On the one hand, reactor and/or dehydrogenating technology can turn round under following air speed: about 1/h is to approximately 1,000/h,For example, about 1/h, 2/h, 3/h, 4/h, 5/h, 8/h, 10/h, 15/h, 20/h, 25/h, 30/h, 35/h, 40/h, 45/h, 50/h,55/h、60/h、65/h、70/h、75/h、80/h、90/h、100/h、150/h、200/h、250/h、300/h、350/h、400/h、450/h, 500/h, 550/h, 600/h, 650/h, 700/h, 750/h, 800/h, 850/h, 900/h, 950/h or 1,000/h; Approximately100/h is to approximately 1,000/h; About 250/h is to approximately 1,000/h; Or about 500/h is to approximately 1,000/h, this depends on and for example usedThe temperature of special catalyst and reactor and/or catalyst bed. On the one hand, reactor and/or dehydrogenating technology can be approximately 520DEG C to approximately 650 DEG C, for example, approximately 520 DEG C, 530 DEG C, 540 DEG C, 550 DEG C, 560 DEG C, 570 DEG C, 580 DEG C, 590 DEG C, 600 DEG C, 610DEG C, turn round at the temperature of 620 DEG C, 630 DEG C, 640 DEG C or 650 DEG C. It should be noted that herein the sky of enumerating for hydrogenation and dehydrogenation reactionSpeed and temperature are intended to illustrate, and have no intention to limit. Therefore, be also intended to comprise that these values than enumerating are low or high hereinValue.

On the other hand, reactor design of the present invention can show following pressure drop during operation: approximately 0.05 bar extremelyApproximately 100 bar, for example, approximately 0.05 bar, 0.1 bar, 0.5 bar, 1 bar, 2 bar, 3 bar, 4 bar, 5 bar, 8 bar, 10 bar, 15 bar, 20 bar, 25Bar, 30 bar, 35 bar, 40 bar, 45 bar, 50 bar, 55 bar, 60 bar, 65 bar, 70 bar, 75 bar, 80 bar, 85 bar, 90 bar, 95 bar or 100Bar. In other respects, reactor of the present invention design can show following pressure drop during operation: approximately 5 bar extremely approximately 100 bar,Approximately 10 bar are to approximately 100 bar, approximately 40 bar to approximately 100 bar, approximately 0.05 bar to approximately 50 bar, or extremely approximately 10 bar of approximately 0.05 bar, or approximately 0.05Bar is to approximately 5 bar.

Similarly, reactor design of the present invention can for example be transported in hydrogenation and/or dehydrogenating technology under following pressureTurn: about 1psig is to about 500psig, for example, about 1psig, 5psig, 15psig, 25psig, 35psig, 45psig, 55psig,75psig、95psig、115psig、135psig、155psig、175psig、195psig、215psig、235psig、255psig、275psig、295psig、315psig、335psig、355psig、375psig、395psig、415psig、435psig, 455psig, 475psig or 500psig. In other respects, reactor of the present invention and/or technique can be in following pressuresUnder power, turn round: about 50psig is to about 500psig, about 100psig to about 500psig, about 200psig to about 500psig, approximately1psig is to about 400psig, about 1psig to about 100psig, or about 1psig is to about 10psig. More on the one hand, reactor and/Or technique can turn round under other pressure high or low in any value than specifically enumerating herein, and the present invention has no intention limitationIn any particular pressure value or scope.

On the other hand, reactor of the present invention and/or technique can be utilized the catalyst with following average surface area:About 15m²/ g is to about 650m²/ g, for example, about 15m²/g、20m²/g、25m²/g、30m²/g、35m²/g、40m²/g、50m²/g、75m²/g、100m²/g、125m²/g、150m²/g、175m²/g、200m²/g、225m²/g、250m²/g、275m²/g、300m²/g、325m²/g、350m²/g、375m²/g、400m²/g、425m²/g、450m²/g、475m²/g、500m²/g、525m²/g、550m²/g、575m²/g、600m²/g、625m²/ g or 650m²/ g; Or about 20m²/ g is to about 650m²/ g; Be greater than about 20m²/ g is to about 650m²/g；About 25m²/ g is to about 650m²/ g; About 30m²/ g is to about 650m²/ g; About 50m²/ g is to about 650m²/ g; About 100m²/ g is to about 650m²/G; Or about 25m²/ g is to about 500m²/ g. Similarly, catalyst can comprise the porous zeolite with following average cell size and carriesBody: approximately Extremely approximatelyFor example, approximately 19 orApproximatelyExtremely approximatelyApproximatelyExtremely approximatelyApproximatelyExtremely approximatelyOr approximatelyExtremely approximatelyIn its other partyFace, catalyst can comprise the mesoporous carrier with following average cell size: approximatelyExtremely approximatelyFor example, approximately OrIn other respects, catalyst can comprise the mesoporous carrier with following average cell size: approximatelyExtremely approximatelyApproximatelyExtremely approximatelyApproximatelyExtremely approximately ApproximatelyExtremely approximatelyOr approximatelyExtremely approximately?Other aspects, can be used and have the surface area do not enumerated and/or other catalyst and/or the carrier of hole dimension herein, andThe present invention has no intention to be confined to any particular table area and/or the hole dimension of catalyst and/or catalyst carrier.

With reference to accompanying drawing, Fig. 1 illustrates the reactor design with two feed inlet 3,4, and these two feed inlet equallyOr the approximate charging of cutting apart equally to come autonomous import 2. By two feed inlet 3,4, feed material can enter reactor1. Then product, accessory substance and/or unreacted feed material can leave reactor from exporting 5,6, and they exist subsequentlyDownstream group is synthesized single stream 7. Then stream from combination outlet 7 can be led to other unit, be directed to have identical orThe independent reactor of different designs, or be directed to collection container. The use of multiple imports can facilitate half as shown in Figure 1Batch mode of operation, semi-batch operation pattern comes in handy for the catalyst that needs frequent regeneration. Reactor optionally wrapsDraw together and drip dish 8,9, it can help to discharge or reclaim concentrate and/or paraffinic base crude oil. On the other hand, as shown in Figure 2, reactionDevice can be configured to have multiple imports 3,4 and single outlet 10.

The cross-sectional view of reactor that comprises multiple imports 3,4 and multiple outlet 5,6 is shown in Figure 3. In Fig. 3, enterFeed material is delivered to distributor 12,13 by material entry nozzle 3,4, and feed material is uniformly distributed in catalyst by this distributorOn bed 14. Catalyst bed is supported by supporter 15,16. Thermocouple sheath 11 can be used to the temperature of monitoring catalyst bed and effectivelyContingent any focus and/or runaway condition are controlled in ground. In addition, concentrate and/or paraffinic base crude oil can be collected in and drip dishIn 17 and can be collected by independent collection outlet 8, and do not affect the running of reactor.

Reactor 1 optionally comprises the integrated pipe 18 of the temperature for regulating catalyst bed. On the one hand, this type of pipe canBe used for carrying by the cooling water of catalyst bed 14. This type of pipe can be connected to for the import 19 of cooling water with for used coldBut the outlet 20 that water is used, as shown in Figure 4.

Fig. 5 illustrates exemplary headend hydrogenation technique, and wherein two reactors use with arranged in series form, and they are positioned at C₂The downstream of separator and the upstream of demethanator. Fig. 6 illustrates exemplary rear end hydrogenation technique, and wherein two reactors are with parallel connectionCollocation form uses, and they are positioned at demethanator and C₂The downstream of separator.

On the other hand, such as CO, CO₂、O₂And/or the particular type of the given impurity of other impurity or its combination and/orConcentration can change, and this depends on the arrangement of given reactor in technique, for example, settles by front-end technology or rear end technology.More on the one hand, the selection of given catalyst can change similarly, and it is passable to have those skilled in the art of the present disclosureEasily select suitable reactor configurations and/or catalyst for the reaction of expecting.

It will be appreciated that arbitrary in can be aspect many examples non-limiting of method of the present invention and reactor designAspect, is described such as those aspects of enumerating below.

Aspect 1: a kind of reactor being applicable in hydrogenation and/or dehydrogenating technology, described reactor comprises: catalyst bed,Multiple imports for delivery of feed material to catalyst bed, and one or more outlet, wherein said catalyst bed comprisesThere is about 15m²/ g is to about 650m²The catalyst of the surface area of/g, and wherein said reactor can be provided for hydrogenation reactionAbout 500/h is to approximately 50, the air speed of 000/h or for the approximately 1/h of dehydrogenation reaction to approximately 1, at least one in the air speed of 000/h.

Aspect 2: according to the reactor described in aspect 1, it also comprises for by feed material evenly or substantially equablyBe distributed in the one or more distributors in whole catalyst bed.

Aspect 3: according to the reactor described in aspect 1 or 2, wherein said catalyst bed is fixed bed, and it comprises selectivelyHydrogenation and/or dehydrogenation.

Aspect 4: according to the reactor described in any one in aspect 1-3, wherein said catalyst bed is configured to and oneOr multiple catalysts bed supporter contact.

Aspect 5: according to the reactor described in any one in aspect 1-4, described reactor is hydrogenation reactor, and it comprises manyThe individual import for alkene charging, oxygenate charging or its combination.

Aspect 6: according to the reactor described in any one in aspect 1-5, it also comprises for reclaiming concentrate and/or paraffinDripping of base crude oil coiled.

Aspect 7: according to the reactor described in any one in aspect 1-6, it also comprises the appearance that is installed in described reactorOne or more thermocouple sheaths between face and described catalyst bed.

Aspect 8: according to the reactor described in any one in aspect 1-7, it also comprises for regulating described catalyst bedThe device of temperature.

Aspect 9: according to the reactor described in any one in aspect 1-8, wherein said catalyst bed comprises heating and/or coldBut element.

Aspect 10: according to the reactor described in any one in aspect 1-9, wherein said catalyst bed comprises for cooling instituteState the pipe of catalyst bed.

Aspect 11: according to the reactor described in any one in aspect 1-10, wherein said catalyst has about 30m²/ g extremelyAbout 650m²The surface area of/g.

Aspect 12: according to the reactor described in any one in aspect 1-11, it has the air speed at least about 25,000/h.

Aspect 13: according to the reactor described in any one in aspect 1-12, itself and conventional hydrogenation and/or dehydrogenation reactor phaseThan thering is following characteristics: high-speed, low pressure drop, feed material being uniformly distributed or its combination in whole catalyst bed.

Aspect 14: a kind of reactor assembly, it comprises multiple with any one in the aspect 1-12 of arranged in series arranged in formDescribed reactor.

Aspect 15: a kind of reactor assembly, it comprises any one in multiple aspect 1-12 that arrange with collocation form in parallelDescribed reactor.

Aspect 16: a kind of method for dehydrogenating technology, described method comprises by described multiple imports feed materialBe incorporated in aspect 1-12 in the reactor described in any one, make described feed material equably or substantially equably with instituteState catalyst bed and contact to produce product.

Aspect 17: according to the method described in aspect 16, wherein said feed material comprises one or more saturated hydrocarbons, andAt least a portion of wherein said one or more saturated hydrocarbons is converted to alkene.

Aspect 18: according to the method described in aspect 16, the alkene that wherein said product comprises purifying.

Aspect 19: a kind of method for hydrogenation technique, described method comprises by described multiple imports feed materialBe incorporated in aspect 1-12 in the reactor described in any one, make described feed material equably or substantially equably with instituteState catalyst bed and contact to produce product.

Aspect 20: according to the method described in aspect 19, wherein said feed material comprises acetylene, and wherein said reactionProduct comprises alkene.

Aspect 21: according to the method described in aspect 16, wherein said reactor provides about 1/h to approximately 1, the air speed of 000/h.

Aspect 22: according to the method described in aspect 19, wherein said reactor provides about 500/h to approximately 50, the sky of 000/hSpeed.

Aspect 23: according to the method described in aspect 16 or 19, wherein said reactor shows approximately 0.05 to approximately 100 barPressure drop.

Aspect 24: according to the method described in aspect 16 or 19, wherein said reactor provides and changes compared with popular response deviceThe kind control to runaway reaction.

Aspect 25: according to the method described in aspect 16 or 19, wherein multiple reactors connect to carry with arranged in series formRemove system for front end acetylene.

Aspect 26: according to the method described in aspect 16 or 19, wherein multiple reactors connect to carry with collocation form in parallelRemove system for rear end acetylene.

One of ordinary skill in the art would recognize that, can be to the present invention in the situation that not deviating from scope of the present invention or spiritMake various amendments and change. Those skilled in the art can show after considering description of the present invention disclosed herein and putting into practiceAnd easily insight is expected other embodiments of the present invention. Description and embodiment are only considered as exemplary, real model of the present inventionEnclose with spirit and pointed out by appended claims.

Claims

1. be applicable to the reactor in hydrogenation and/or dehydrogenating technology, described reactor comprises:

A. catalyst bed;

B. many imports, it is for delivery of extremely described catalyst bed of feed material; And

C. one or more outlets,

Wherein said catalyst bed comprises having about 15m²/ g is to about 650m²The catalyst of the surface area of/g, and wherein said anti-Answer approximately 500/h that device can be provided for hydrogenation reaction to approximately 50, the air speed of 000/h or for the approximately 1/h of dehydrogenation reaction to approximately 1,At least one in the air speed of 000/h.

2. reactor according to claim 1, it also comprises for by described feed material evenly or substantially equablyBe distributed in the one or more distributors in whole described catalyst bed.

3. reactor according to claim 1 and 2, wherein said catalyst bed is fixed bed, it comprises selective hydrogenationAnd/or dehydrogenation.

4. according to the reactor described in any one in claim 1-3, wherein said catalyst bed is configured to a kind of or manyPlant the contact of catalyst bed supporter.

5. according to the reactor described in any one in claim 1-4, described reactor is hydrogenation reactor, and it comprises multiple pinsTo the import of alkene charging, oxygenate charging or its combination.

6. according to the reactor described in any one in claim 1-5, it also comprises for reclaiming concentrate and/or paraffinic base is formerDripping of oil coiled.

7. according to the reactor described in any one in claim 1-6, its also comprise the outer surface that is installed in described reactor withOne or more thermocouple sheaths between described catalyst bed.

8. according to the reactor described in any one in claim 1-7, it also comprises the temperature for regulating described catalyst bedDevice.

9. according to the reactor described in any one in claim 1-8, wherein said catalyst bed comprises heating and/or cooling unitPart.

10. according to the reactor described in any one in claim 1-9, wherein said catalyst bed comprises described in cooling urgesThe pipe of agent bed.

11. according to the reactor described in any one in claim 1-10, and wherein said catalyst has about 30m²/ g extremely approximately650m²The surface area of/g.

12. according to the reactor described in any one in claim 1-11, and it has the air speed at least about 25,000/h.

13. according to the reactor described in any one in claim 1-12, and it is tool compared with conventional hydrogenation and/or dehydrogenation reactorThere is following characteristics: high-speed, low pressure drop, feed material being uniformly distributed or its combination in described whole catalyst bed.

14. 1 kinds of reactor assemblies, it comprises multiple with described in any one in the claim 1-12 of arranged in series arranged in formReactor.

15. 1 kinds of reactor assemblies, it comprises multiple with described in any one in the claim 1-12 of collocation form layout in parallelReactor.

16. 1 kinds of methods for dehydrogenating technology, described method comprises by described multiple imports feed material is incorporated into powerProfit requires in 1-12, in the reactor described in any one, described feed material to be urged equably or substantially equably with describedAgent bench grafting touches to produce products of dehydrogenation reactions.

17. methods according to claim 16, wherein said feed material comprises one or more saturated hydrocarbons, and whereinAt least a portion of described one or more saturated hydrocarbons is converted to alkene.

18. methods according to claim 16, the alkene that wherein said product comprises purifying.

19. 1 kinds of methods for hydrogenation technique, described method comprises by described multiple imports feed material is incorporated into powerProfit requires in 1-12, in the reactor described in any one, described feed material to be urged equably or substantially equably with describedAgent bench grafting touches to produce hydrogenation reaction product.

20. methods according to claim 19, wherein said feed material comprises acetylene, and wherein said productComprise alkene.

21. methods according to claim 16, wherein said reactor provides about 1/h to approximately 1, the air speed of 000/h.

22. methods according to claim 19, wherein said reactor provides about 500/h to approximately 50, the air speed of 000/h.

23. methods according to claim 16, wherein said reactor shows approximately 0.05 pressure drop to approximately 100 bar.

24. methods according to claim 19, wherein said reactor shows approximately 0.05 pressure drop to approximately 100 bar.

25. methods according to claim 16, wherein said reactor provide compared with popular response device improvement to loseThe control of control reaction.

26. methods according to claim 19, wherein said reactor provide compared with popular response device improvement to loseThe control of control reaction.

27. methods according to claim 16, wherein multiple reactors connect to provide front end second with arranged in series formAlkynes is removed system.

28. methods according to claim 19, wherein multiple reactors connect to provide front end second with arranged in series formAlkynes is removed system.

29. methods according to claim 16, wherein multiple reactors connect to provide rear end second with collocation form in parallelAlkynes is removed system.

30. methods according to claim 19, wherein multiple reactors connect to provide rear end second with collocation form in parallelAlkynes is removed system.